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HomeMy WebLinkAboutNC0000396_J15050803_Speciation_20150823+ DUKE Analytical Laboratory Page 1of31 ENERGY Order Number: Project Name: Customer Name(s): Customer Address: Lab Contact: Report Authorized By: (Signature) Program Comments: 13339 Hagers Ferry Road Huntersville, NC 28078-7929 McGuire Nuclear Complex - MG03A2 Phone: 980-875-5245 Fax: 980-875-4349 Order Summary Report J15050803 ASHEVILLE - AB GW ASSESSMENT SPECIATION Todd Plating, Kathy Webb, John Toepfer, Tim Hunsucker 200 CP and L Drive Arden, NC 28704 Peggy Kendall Phone: �} p peggy.kendall@duke- energy.com energy.com Date: F 2015.06.17 11:41:06 -04'00' Peggy Kendall Please contact the Program Manager (Peggy Kendall) with any questions regarding this report. Data Flags & Calculations: 6/16/2015 Any analytical tests or individual analytes within a test flagged with a Qualifier indicate a deviation from the method quality system or quality control requirement. The qualifier description is found at the end of the Certificate of Analysis (sample results) under the qualifiers heading. All results are reported on a dry weight basis unless otherwise noted. Subcontracted data included on the Duke Certificate of Analysis is to be used as information only. Certified vendor results can be found in the subcontracted lab final report. Duke Energy Analytical Laboratory subcontracts analyses to other vendor laboratories that have been qualified by Duke Energy to perform these analyses except where noted. Data Package: This data package includes analytical results that are applicable only to the samples described in this narrative. An estimation of the uncertainty of measurement for the results in the report is available upon request. This report shall not be reproduced, except in full, without the written consent of the Analytical Laboratory. Please contact the Analytical laboratory with any questions. The order of individual sections within this report is as follows: Job Summary Report, Sample Identification, Technical Validation of Data Package, Analytical Laboratory Certificate of Analysis, Analytical Laboratory QC Reports, Sub -contracted Laboratory Results, Customer Specific Data Sheets, Reports & Documentation, Customer Database Entries, Test Case Narratives, Chain of Custody (COC) Certification: The Analytical Laboratory holds the following State Certifications : North Carolina (DENR) Certificate #248, South Carolina (DHEC) Laboratory ID # 99005. Contact the Analytical Laboratory for definitive information about the certification status of specific methods. Sample ID's & Descriptions: Collection Sample ID Plant/Station Date and Time Collected By Sample Description 2015016676 ASHEVILLE 26 -May -15 2:15 PM Synterra Equipment Blank 2015016678 ASHEVILLE 26 -May -15 10:32 AM Synterra ABMW-04 2015016679 ASHEVILLE 26 -May -15 10:35 AM Synterra ABMW-05S 2015016680 ASHEVILLE 26 -May -15 12:54 PM Synterra ABMW-04D 2015016681 ASHEVILLE 26 -May -15 2:18 PM Synterra ABMW-05D 5 Total Samples Page 2 of 31 Technical Validation Review Checklist: COC and .pdf report are in agreement with sample totals Yes No and analyses (compliance programs and procedures). All Results are less than the laboratory reporting limits. ❑ Yes F./] No All laboratory QA/QC requirements are acceptable.❑ Yes ❑ No Report Sections Included: U Job Summary Report ❑ Sample Identification n Technical Validation of Data Package ❑ Analytical Laboratory Certificate of Analysis ❑ Analytical Laboratory QC Report Page 3 of 31 Sub -contracted Laboratory Results ❑ Customer Specific Data Sheets, Reports, & Documentation ❑ Customer Database Entries 66 Chain of Custody [I/0] Electronic Data Deliverable (EDD) Sent Separately Reviewed By: Peggy Kendall Date: 6/16/2015 Certificate of Laboratory Analysis Page 4 of 31 This report shall not be reproduced, except in full. Order # J15050803 Site: Equipment Blank Collection Date: 26 -May -15 2:15 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015016676 Matrix: GW—WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15050803 Site: ABMW-04 Collection Date: 26 -May -15 10:32 AM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015016678 Matrix: GW—WW Page 5 of 31 Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15050803 Site: ABMW-05S Collection Date: 26 -May -15 10:35 AM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015016679 Matrix: GW—WW Page 6 of 31 Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15050803 Site: ABMW-04D Collection Date: 26 -May -15 12:54 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015016680 Matrix: GW—WW Page 7 of 31 Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis Page 8 of 31 This report shall not be reproduced, except in full. Order # J15050803 Site: ABMW-05D Collection Date: 26 -May -15 2:18 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015016681 Matrix: GW—WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Page 9 of 31 BRO�©KS RAND LABS MEANINGFUL METALS DATA June 10, 2015 Jay Perkins Duke Energy Analytical Laboratory Mail Code MGO3A2 (Building 7405) 13339 Hagers Ferry Rd. Huntersville, NC 28078 (704) 875-5245 Project: Duke Asheville Plant (LIMS# J15050803) Mr. Perkins, Attached is the report associated with five (5) aqueous samples submitted for hexavalent chromium, selenium speciation, arsenic speciation, iron speciation, and manganese speciation analyses on May 26, 2015. The samples were received in a sealed cooler at 0.5°C on May 27, 2015. Hexavalent chromium analysis was performed by ion chromatography inductively coupled plasma dynamic reaction cell mass spectrometry (IC -ICP -DRC -MS). Selenium speciation and arsenic speciation analyses were performed via ion chromatography inductively coupled plasma collision reaction cell mass spectrometry (IC -ICP -CRC -MS). All samples requesting iron speciation analysis were analyzed by spectrophotometry. Mn (II) analysis was performed via IC -ICP -CRC -MS. Mn(IV) analysis were performed via digestion and subsequent analysis by inductively coupled plasma triple quadrupole mass spectrometry (ICP-QQQ-MS). Any issues associated with the analyses are addressed in the following report. If you have any questions, please feel free to contact me at your convenience. Sincerely, it L7�-- Jeremy Maute Project Manager Brooks Rand Labs, LLC 3958 6th Ave NW • Seattle, WA 98107 • T: 206-632-6206 • F: 206-632-6017 • www.brooksrand.com • brl@brooksrand.com Brooks Rand Labs, LLC Report prepared for: Jay Perkins Duke Energy Analytical Laboratory Mail Code MGO3A2 (Building 7405) 13339 Hagers Ferry Rd. Huntersville, NC 28078 Project: Duke Asheville Plant (LIMS# J15050803) June 10, 2015 1. Sample Reception Page 10 of 31 Five (5) aqueous samples were submitted for hexavalent chromium, selenium speciation, arsenic speciation, iron speciation, and manganese speciation analyses on May 26, 2015. All samples were received in acceptable condition on May 27, 2015 in a sealed container at 0.5°C. All samples were received in a laminar flow clean hood, void of trace metals contamination and ultra -violet radiation, and were designated discrete sample identifiers. An aliquot of each sample submitted for hexavalent chromium analysis was decanted into a clean polypropylene tube. All hexavalent chromium sample fractions were stored in a secure refrigerator maintained at a temperature of 4°C, until the analyses could be performed. An aliquot of each sample requiring selenium speciation evaluation was filtered (0.45µm) and each filtrate was stored in a secure, monitored cryofreezer (maintained at a temperature of -80°C) until selenium speciation analysis could be performed. An aliquot of each sample submitted for arsenic speciation analysis was filtered (0.45µm) into a polypropylene centrifuge tube; all filtrates and original bottles were then stored in a secure, monitored refrigerator (maintained at a temperature of <6°C) until the analyses could be performed. The sample fractions requesting iron speciation analysis were stored in a secure, monitored refrigerator (maintained at a temperature of <6°C) until the analyses could be performed. An aliquot of each filtered sample submitted for manganese speciation analysis was decanted into a polypropylene centrifuge tube for Mn(II) analysis. These fractions were stored in a secure, monitored refrigerator (maintained at a temperature of <6°C) until the analyses could be performed. Subsequently, the original bottles (filtered and unfiltered fractions) intended for Mn speciation were preserved to pH < 2 with concentrated HNO3 and then stored in a Page 11 of 31 secure polyethylene container, known to be free from trace metals contamination, until the digestion could be performed. 2. Sample Preparation All sample preparation is performed in laminar flow clean hoods known to be free from trace metals contamination. All applied water for dilutions and sample preservatives are monitored for contamination to account for any biases associated with the sample results. Hexavalent Chromium Analysis by IC -ICP -DRC -MS Prior to analysis, an aliquot of each sample was filtered with a syringe filter (0.45µm) and injected directly into a sealed autosampler vial. No further sample preparation was performed as any chemical alteration of a sample may shift the equilibrium of the system, resulting in changes in speciation ratios. Selenium Speciation Analysis by IC -ICP -CRC -MS Prior to analysis, an aliquot of each sample was filtered with a syringe filter (0.45µm) and injected directly into a sealed autosampler vial. No further sample preparation was performed as any chemical alteration of a sample may shift the equilibrium of the system, resulting in changes in speciation ratios. Arsenic Speciation Analysis by IC -ICP -CRC -MS An aliquot of each sample was filtered directly into a sealed autosampler vial. No further sample preparation was performed as a buffered EDTA solution was provided by Brooks Rand Labs for field -preservation of the submitted samples. Iron Speciation Analysis by Spectrophotometry No sample preparation was required as a de- gassed HCL solution was provided by Brooks Rand Labs for field -preservation of the submitted samples. Manganese Mn(II) Analysis by IC -ICP -CRC -MS An aliquot of each sample was filtered (0.45µm) directly into an autosampler vial for Mn(II) analysis. No additional sample preparation was performed as any chemical alteration of the samples may shift the equilibrium of the system resulting in changes in speciation ratios. Manganese Mn(IV) Analysis by ICP-QQQ-MS Each filtered and unfiltered sample submitted for Mn speciation analysis was preserved with 1% HNO3 (v/v) upon sample receipt. Each sample fraction was then further digested on a hotblock apparatus with aliquots of 50% HNO3 (v/v) and 50% HCl (v/v), in accordance with the digestion procedure specified in EPA Method 200.8. All resulting sample digests were analyzed for total manganese via inductively coupled plasma triple quadrupole mass spectrometry (ICP-QQQ-MS). Page 12 of 31 3. Sample Analysis All sample analysis is preceded by a minimum of a five -point calibration curve spanning the entire concentration range of interest. Calibration curves are performed at the beginning of each analytical day. All calibration curves, associated with each species of interest, are standardized by linear regression resulting in a response factor. All sample results are instrument blank corrected to account for any operational biases associated with the analytical platform. Prior to sample analysis, all calibration curves are verified using second source standards which are identified as initial calibration verification standards (ICV). Ongoing instrument performance is identified by the analysis of continuing calibration verification standards (CCV) and continuing calibration blanks (CCB) at a minimum interval of every ten analytical runs. Hexavalent Chromium Analysis by IC -ICP -DRC -MS Each sample for hexavalent chromium analysis was analyzed by ion chromatography inductively coupled plasma dynamic reaction cell mass spectrometry (IC -ICP -DRC -MS) on June 5, 2015. An aliquot of each sample is injected onto an anion exchange column and mobilized by a basic (pH > 7) gradient. The eluting chromium species are then introduced into a radio frequency (RF) plasma where energy -transfer processes cause desolvation, atomization, and ionization. The ions are extracted from the plasma through a differentially -pumped vacuum interface and travel through a pressurized chamber (DRC) containing a reaction gas which preferentially reacts with interfering ions of the same target mass to charge ratios (m/z). A solid-state detector detects ions transmitted through the mass analyzer and the resulting current is processed by a data handling system. Retention times for each eluting species are compared to known standards for species identification. Selenium Speciation Analysis by IC -ICP -CRC -MS Each sample for selenium speciation analysis was analyzed by ion chromatography inductively coupled plasma collision reaction cell mass spectrometry (IC -ICP -CRC -MS) on June 3, 2015. An aliquot of each sample is injected onto an anion exchange column and mobilized by a basic (pH > 7) gradient. The eluting selenium species are then introduced into a radio frequency (RF) plasma where energy -transfer processes cause desolvation, atomization, and ionization. The ions are extracted from the plasma through a differentially -pumped vacuum interface and travel through a pressurized chamber (CRC) containing a reaction gas which preferentially reacts with interfering ions of the same target mass to charge ratios (m/z). A solid-state detector detects ions transmitted through the mass analyzer and the resulting current is processed by a data handling system. Retention times for each eluting species are compared to known standards for species identification. Page 13 of 31 Arsenic Speciation Analysis by IC -ICP -CRC -MS Each sample was analyzed for arsenic speciation via ion chromatography inductively coupled plasma collision reaction cell mass spectrometry (IC -ICP -CRC -MS) on June 3, 2015. Aliquots of each sample are injected onto an anion exchange column and eluted isocratically. The eluting arsenic species are then introduced into a radio frequency (RF) plasma where energy -transfer processes cause desolvation, atomization, and ionization. The ions are extracted from the plasma through a differentially -pumped vacuum interface and travel through a pressurized chamber (CRC) containing a specific collision gas. Polyatomic interferences, due to their inherently larger size, collide more frequently with the collision gas and therefore may be separated from the analyte of interest via kinetic energy discrimination (KED). A solid-state detector detects ions transmitted through the mass analyzer on the basis of their mass -to -charge ratio (m/z), and the resulting current is processed by a data handling system. Retention times for each eluting species are compared to known standards for species identification. Iron Speciation Analysis by Spectrophotometry All samples submitted for Fe speciation quantification were analyzed on May 28, 2015, and in accordance with the scientifically accepted method outlined by: Stookey, L.L., (1970). "Ferrozine - A new spectrophotometric reagent for iron", Anal.Chem., 42:779-81. Manganese Mn(LI) Analysis by IC -ICP -CRC -MS All samples for Mn(II) analysis were analyzed by ion chromatography inductively coupled plasma collision reaction cell mass spectrometry (IC -ICP -CRC -MS) on June 4, 2015. Aliquots of each sample are injected onto an anion exchange column and mobilized by an acidic (pH < 7) gradient. An ion pairing agent provides a dynamic ion exchange mechanism for the cationic manganese species on the chromatographic column. The differences in the affinity of manganese species towards the ion pair agent and the column results in separation. The eluting selenium species are then introduced into a radio frequency (RF) plasma where energy -transfer processes cause desolvation, atomization, and ionization. The ions are extracted from the plasma through a differentially -pumped vacuum interface and travel through a pressurized chamber (CRC) containing a reaction gas which preferentially reacts with interfering ions of the same target mass to charge ratios (m/z). A solid-state detector detects ions transmitted through the mass analyzer and the resulting current is processed by a data handling system. Retention times for each eluting species are compared to known standards for species identification. Manganese Mn(IV) Analysis by ICP-QQQ-MS All samples submitted for Mn speciation quantitation were analyzed by inductively coupled plasma triple quadrupole mass spectrometry (ICP-QQQ-MS) on June 5, 2015. Aliquots of each sample digest are introduced into a radio frequency (RF) plasma where energy -transfer processes cause desolvation, atomization, and ionization. The ions are extracted from the plasma through a Page 14 of 31 differentially -pumped vacuum interface and travel through an initial quadrupole (Q 1), which filters the target masses prior to their entrance into a second chamber. The second chamber contains specific reactive gasses or collision gasses that preferentially react either with interfering ions of the same target mass to charge ratios (m/z) or with the target analyte, producing an entirely different mass to charge ratio (m/z) which can then be differentiated from the initial interferences. The ions then exit the collision/reaction cell into and additional quadrupole (Q2). A solid-state detector detects ions transmitted through the mass analyzer, on the basis of their mass -to -charge ratio (m/z), and the resulting current is processed by a data handling system. 4. Analytical Issues No significant analytical issues were encountered. All quality control parameters associated with the samples were within acceptance limits. The preparation blanks associated with the iron speciation samples were not analyzed. An equipment blank sample was received with the client samples. The equipment blank sample yielded negligible Fe(II) and Fe(III) results, demonstrating the absence of any significant iron contamination due to sampling. The iron speciation results for the equipment blank sample should be taken into consideration when evaluating the results. All samples were analyzed for iron speciation on May 28, 2015. The analysis took place from 11:30 to 18:00. It is likely that reagents were not added to the client samples ABMW-04 (collected 5/26/2015 10:32) and ABMW-05 S (collected 5/26/2015 10:35) within the prescribed 48 hour hold time. Accordingly, the Fe(II) results associated with two samples should be considered estimated. Several Mn(II) results were greater than the value of the associated high calibration standard. A linear range verification standard was analyzed at 2000 µg/L. The Mn(II) recovery for the linear range verification standard was acceptable, at 100.1%, demonstrating that the linear range of the analytical platform extended to 2000 µg/L for Mn(II). All reported Mn(II) results were less than 2000 µg/L with the dilutions at the instrument factored in, and thus were within the linear range demonstrated by the linear range verification standard. No corrective actions were necessary. For the Mn(II) analytical run, a client sample from another reception date (batch QC) was analyzed as the quality control sample. The matrix spike sample and matrix spike duplicate sample (MS/MSD) spike recoveries for Mn(II) were below the lower control limit of 75%, at -494.8% and -541.0%, respectively. The native Mn(II) concentration in the quality control sample was significantly greater than the spiking level. Acceptable spike recoveries are often not realized when the ambient level analyte concentration is greater than the spiking level. No qualification of data was necessary. Page 15 of 31 Mn(IV) is quantified by analyzing the water samples for total Mn and dissolved Mn. Mn(IV) is operationally defined as the difference between the filtered and unfiltered total Mn concentrations, since it is thermodynamically favored to be in the form of a precipitate. For the Mn(IV) analysis, several total and dissolved Mn results were greater than the value of the associated high calibration standard. A linear range verification standard was analyzed at 500 µg/L. The Mn recovery for the linear range verification standard was acceptable, at 100.4%, demonstrating that the linear range of the analytical platform extended to 500 µg/L for Mn. All reported total and dissolved Mn results were less than 500 µg/L with the dilutions at the instrument factored in; all results were within the linear range demonstrated by the linear range verification standard. No corrective actions were necessary. The estimated method detection limit (eMDL) for hexavalent chromium is generated from replicate analyses of the lowest standard in the calibration curve. The eMDL values for selenite, selenate, and selenocyanate are generated from replicate analyses of the lowest standard in the calibration curve. Not all selenium species are present in preparation blanks; therefore, eMDL calculations based on preparation blanks are artificially biased low. The eMDL values for methylseleninic acid and selenomethionine are calculated from the average eMDL of selenite, selenate, and selenocyanate. The calibration does not contain methylseleninic acid or selenomethionine due to impurities in these standards which would bias the results for other selenium species. The eMDL values for arsenite, arsenate, and dimethylarsinic acid are generated using the standard deviation of replicate analyses of the lowest standard in the calibration curve. The eMDL for monomethylarsonic acid is calculated from the average eMDL of the three arsenic species contained in the calibration (i.e., arsenite, arsenate, and dimethylarsinic acid); the calibration and CCVs do not contain monomethylarsonic acid due to impurities in this standard which would bias the results for other arsenic species. The eMDL value for Fe(II) has been generated from replicate analyses of the lowest standard in the calibration curve. The eMDL value for total recoverable Fe was set at 1/3 the value of the associated reporting limit since the standard deviation associated with the replicate analyses of the lowest standard in the calibration curve was zero. The eMDL for Mn(II) has been generated from replicate analyses of the lowest standard in the calibration curve. The eMDL values for Mn(IV) been calculated using the standard deviation of the method blanks prepared and analyzed concurrently with the submitted samples. Page 16 of 31 If you have any questions or concerns regarding this report, please feel free to contact me. Sincerely, it L7S�-- Jeremy Maute Project Manager Brooks Rand Labs, LLC Speciation Results for Duke Energy Project Name: Duke Asheville Plant Contact: Jay Perkins LIMS# J15050803 Date: June 10, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Samale Results H Page 17 of 31 Sample ID Cr(VI) Se(IV) Se(VI) SeCN McSe(IV) SeMe Unknown Se Species (n) Equipment Blank 0.008 ND (< 0.12) ND (< 0.16) ND (< 0.072) ND (< 0.12) ND (< 0.12) 0 (0) ABMW-04 ND (< 0.007) 0.13 ND (< 0.16) 0.129 ND (< 0.12) ND (< 0.12) 0 (0) ABMW-05 S 0.017 ND (< 0.12) ND (< 0.16) ND (< 0.072) ND (< 0.12) ND (< 0.12) 0 (0) ABMW-04 D 0.020 ND (< 0.12) ND (< 0.16) ND (< 0.072) ND (< 0.12) ND (< 0.12) 0 (0) ABMW-05 D 0.016 ND (< 0.12) ND (< 0.16) ND (< 0.072) ND (< 0.12) ND (< 0.12) 0 (0) All results reflect the applied dilution and are reported in lag/L ND = Not detected at the applied dilution SeCN = Selenocyanate McSe(IV) = Methylseleninic acid SeMe = Selenomethionine Unknown Se Species = Total concentration of all unknown Se species observed by IC -ICP -MS n = number of unknown Se species observed Page 18 of 31 Speciation Results for Duke Energy Project Name: Duke Asheville Plant Contact: Jay Perkins LIMS# J15050803 Date: June 10, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Sample Results (2) All results reflect the applied dilution and are reported in pg/L ND = Not detected at the applied dilution MMAs = monomethylarsonic acid DMAs = dimethylarsinic acid Unknown As Species = Total concentration of all unknown As species observed by IC -ICP -MS Unknown As Sample ID As(III) As(V) MMAs DMAs Species Equipment Blank ND (< 0.018) ND (< 0.11) ND (< 0.054) ND (< 0.038) ND (< 0.054) ABMW-04 310 341 ND (< 0.27) ND (< 0.19) ND (< 0.27) ABMW-05 S 0.166 ND (< 0.11) ND (< 0.054) ND (< 0.038) ND (< 0.054) ABMW-04 D 1.11 0.23 ND (< 0.054) ND (< 0.038) 0.294 ABMW-05 D 0.177 ND (< 0.11) ND (< 0.054) ND (< 0.038) ND (< 0.054) All results reflect the applied dilution and are reported in pg/L ND = Not detected at the applied dilution MMAs = monomethylarsonic acid DMAs = dimethylarsinic acid Unknown As Species = Total concentration of all unknown As species observed by IC -ICP -MS Page 19 of 31 Speciation Results for Duke Energy Project Name: Duke Asheville Plant Contact: Jay Perkins LIMS# J15050803 Date: June 10, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Samale Results (3 Sample ID Fe(II) Fe(III)* Mn (II) Mn(IV)** Equipment Blank ND (< 3.6) 6.7 ND (< 0.86) ND (< 0.098) ABMW-04 14.6 43.5 128 ND (< 0.098) ABMW-05 S 3280 1300 648 ND (< 0.098) ABMW-04 D 4990 ND (< 330) 6600 ND (< 0.098) ABMW-05 D 13500 2600 408 6.13 All results reflect the applied dilution and are reported in Ng/L ND = Not detected at the applied dilution *Fe(III) operationally defined as the difference between total recoverable Fe and Fe(II) *Mn(IV) operationally defined as the difference between total and dissolved Mn Speciation Results for Duke Energy Project Name: Duke Asheville Plant Contact: Jay Perkins LIMS# J15050803 Date: June 10, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Preparation Blank Summary (1 Page 20 of 31 Analyte (Pg/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 5x RL 5x eMDL 50x RL 50x Cr(VI) 0.002 0.005 0.001 0.005 0.0034 0.0019 0.001 0.007 0.050 - - Se(IV) -0.05 -0.05 -0.05 -0.05 -0.05 0.00 0.002 - - 0.12 0.50 Se(VI) -0.05 -0.05 -0.05 -0.05 -0.05 0.00 0.003 - - 0.16 0.50 SeCN 0.00 0.00 0.00 0.00 0.00 0.00 0.001 - - 0.072 0.46 McSe(IV) 0.00 0.00 0.00 0.00 0.00 0.00 0.002 - - 0.12 0.49 SeMe 0.00 0.00 0.00 0.00 0.00 0.00 0.002 - - 0.12 0.49 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Quality Control Summary - Preparation Blank Summary (2) Analyte (Pg/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 10x RL 10x eMDL 50x RL 50x As(III) 0.000 0.000 0.000 0.000 0.000 0.000 0.002 0.018 0.20 0.089 1.0 As(V) 0.00 0.00 0.00 0.00 0.00 0.00 0.011 0.11 0.20 0.53 1.0 MMAs 0.000 0.000 0.000 0.000 0.000 0.000 0.005 0.054 0.20 0.27 1.0 DMAs 0.000 0.000 0.000 0.000 0.000 0.000 0.004 0.038 0.21 0.19 1.0 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Page 21 of 31 Speciation Results for Duke Energy Project Name: Duke Asheville Plant Contact: Jay Perkins LIMS# J15050803 Date: June 10, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Qualitv Control Summary - Preparation Blank Summary (3 Analyte (tag/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL** eMDL 1x RL 1x eMDL 50x RL 50x Fe(II) * * * 3.6 3.6 20 180 1000 Total Fe * * * * 6.7 6.7 20 330 1000 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Preparation blanks for Fe speciation were not analyzed. See narrative **Please see narrative regarding eMDL calculations Qualitv Control Summary - Preparation Blank Summary (3 Analyte (tag/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 10x RL 10x eMDL 25x RL 25x Mn (11) 0.24 0.05 0.02 0.72 0.10 0.32 0.086 0.86 5.0 - - Total Mn 0.057 0.005 0.064 0.004 0.042 0.033 0.000 - - 0.098 1.0 Diss Mn 0.000 -0.003 0.042 0.023 0.013 0.021 0.000 - - 0.063 1.0 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Page 22 of 31 Speciation Results for Duke Energy Project Name: Duke Asheville Plant Contact: Jay Perkins LIMS# J15050803 Date: June 10, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Certified Reference Materials (1 Analyte (Ng/L) CRM True Value Result Recovery Cr(VI) LCS 2.002 1.781 89.0 Se(IV) LCS 10.00 9.967 99.7 Se(VI) LCS 10.00 10.28 102.8 SeCN LCS 8.92 8.896 99.7 McSe(IV) LCS 6.47 6.560 101.4 SeMe LCS 9.32 9.431 101.2 Quality Control Summary - Certified Reference Materials (2) Analyte (pg/L) CRM True Value Result Recovery As(III) LCS 5.00 5.824 116.5 As(V) LCS 5.00 5.244 104.9 MMAs LCS 5.07 5.657 111.5 DMAs LCS 3.63 3.700 102.1 Quality Control Summary - Certified Reference Materials (3) Analyte (pg/L) CRM True Value Result Recovery Fe(II) ICV 500.0 442.8 88.6 Total Fe LCS 500.0 460.0 92.0 Mn (II) LCS 1.00 1.053 105.3 Total Mn TMDA-70.2 312 295.2 94.6 Diss Mn TMDA-70.2 312 308.1 98.7 Page 23 of 31 Speciation Results for Duke Energy Project Name: Duke Asheville Plant Contact: Jay Perkins LIMS# J15050803 Date: June 10, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Matrix Duplicates (1) Analyte (pg/L) Sample ID Rep 1 Rep 2 Mean RPD Cr(VI) Batch QC 0.059 0.060 0.059 0.9 Se(IV) ABMW-05 D ND (< 0.12) ND (< 0.12) NC NC Se(VI) ABMW-05 D ND (< 0.16) ND (< 0.16) NC NC SeCN ABMW-05 D ND (< 0.072) ND (< 0.072) NC NC McSe(IV) ABMW-05 D ND (< 0.12) ND (< 0.12) NC NC SeMe ABMW-05 D ND (< 0.12) ND (< 0.12) NC NC ND = Not detected at the applied dilution NC = Value was not calculated due to one or more concentrations below the eMDL Quality Control Summary - Matrix Duplicates (2) Analyte (pg/L) Sample ID Rep 1 Rep 2 Mean RPD As(III) Batch QC ND (< 0.018) ND (< 0.018) NC NC As(V) Batch QC ND (< 0.11) ND (< 0.11) NC NC MMAs Batch QC ND (< 0.054) ND (< 0.054) NC NC DMAs Batch QC ND (< 0.038) ND (< 0.038) NC NC ND = Not detected at the applied dilution NC = Value was not calculated due to one or more concentrations below the eMDL Page 24 of 31 Speciation Results for Duke Energy Project Name: Duke Asheville Plant Contact: Jay Perkins LIMS# J15050803 Date: June 10, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Matrix Duplicates (3 Analyte (pg/L) Sample ID Rep 1 Rep 2 Mean RPD Fe(II) ABMW-04 14.6 7.3 10.9 66.7* Total Fe ABMW-04 58.1 58.1 58.1 0.0 Mn (II) Batch QC 3291 3258 3274 1.0 Total Mn Batch QC 2834 2689 2762 5.3 Diss Mn Batch QC 2622 2632 2627 0.3 ND = Not detected at the applied dilution NC = Value was not calculated due to one or more concentrations below the eMDL *Associated results were less than the RL Page 25 of 31 Speciation Results for Duke Energy Project Name: Duke Asheville Plant Contact: Jay Perkins LIMS# J15050803 Date: June 10, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Qualitv Control Summary - Matrix Spike/ Matrix Spike Duplicate (1 Analyte (lag/L) Sample ID Spike Conc MS Result Recovery Spike Conc MSD Result Recovery RPD Cr(VI) Batch QC 5.000 4.824 95.3 5.000 5.180 102.4 7.1 Se(IV) ABMW-05 D 251.0 221.2 88.1 251.0 219.1 87.3 1.0 Se(VI) ABMW-05 D 250.0 209.3 83.7 250.0 208.5 83.4 0.4 SeCN ABMW-05 D 228.8 199.6 87.2 228.8 200.1 87.5 0.3 Quality Control Summary - Matrix Spike/ Matrix Spike Duplicate (2) Analyte (lag/L) Sample ID Spike Conc MS Result Recovery Spike Conc MSD Result Recovery RPD As(III) Batch QC 20.00 21.09 105.5 20.00 21.05 105.3 0.2 As(V) Batch QC 20.00 21.07 105.4 20.00 20.99 104.9 0.4 DMAs Batch QC 20.98 22.06 105.2 20.98 22.04 105.0 0.1 Quality Control Summary - Matrix Spike/ Matrix Spike Duplicate (3) Analyte (lag/L) Sample ID Spike Conc MS Result Recovery Spike Conc MSD Result Recovery RPD Fe(I1) ABMW-04 500.0 430.6 83.9 500.0 450.1 87.8 4.4 Total Fe ABMW-04 200.0 225.5 83.7 200.0 247.8 94.9 9.4 Mn (II) Batch QC 50.00 3027 -494.8* 50.00 3004 -541.0* 0.8 Total Mn Batch QC 1000 3633 87.1 1000 3544 78.2 2.5 Diss Mn Batch QC 1000 3549 92.2 1000 3568 94.1 0.6 *Ambient analyte concentration greater than spiking level. See case narrative O o o W� P age 26 of M 0000 Or - M 00 1 V C O c) y G -0 •O 'O 'O 'a 'a � 'O�� '�0� •O � O N N L L 0 L N L N L N L N L L L L vo.ir- oJ 45 .O L:3 32 N a C o vvvvr-a N C �. ti. w o ►. o N N N N N N N N >00 , m r3CII E a 0 ( E o U i v o C N O�� N� C u N w y ° y >. Q— CO L Cl) in co GII �/OL CL Cl)CO�/� V/ OL V/ CL N �/� y/ 00 C u •• Q LL �Q/�i iii ui Q U N LL C C G c C L N U) o E� �• L� O '� 'b •� w "U 1 -3• U U O Q z :D 'r g w GL -0oo CL W O O ca . 1 u L) Ey cn -4. ❑ O C Y y O O Y M :3B 110 H E E 7 O 6. .Oj — �i�]a N O U O U � v v 2 Cl) 2 `d Z Q N 0 0 0 N O 0 0 ai aCCi Ow Z Z Z Q = 0 Z Z Z C L W cm — Z Z 4) Q 9 Q J O t t cl 1 1_ a Cd N N N ti N 0 oo H 1 _45 O .. N Dl - a'�1 C k fl Q z `N'4jZM b Q V` ate. N (a'.', H � N ,c+ i1' \. � C N U C U U �J iuu ^�ww��^�al • •►•� • O 'I J . y age 27 of V 4 � a E n E E E E U Fes-- U H v 0 O 9 C O U v M N uOj v 2 0 p b 102 0;11 v v S Q In V+ v+ 1n Y+ Q Z Q C Y V Q? o 0 M00 N- ea C C C p r0/1 N 0 Z 0 Z 0 Z 0= Z Z Z — A 00� O p C o u w Z 00 M .. ooIt v °' O pp O O O O a O O O N O O ti U r .�-. .�-. +�+ .��. rte. .(D. N U D. C1. 4= 4- w d 4= i� tom- r R,W O y ;F � w ^O N Cl) CO u aCL a O Q U N LLC c CC c V Cl)LL Q U N CC c C CC c ,a^� L v, u C% +J`f O 00 E 0 L L �� u•� o -d >�� b „i ld N w ° .-� U c' a v .� �.. ar a o °Y' v o b �• � P. �„ ! Er V a U cp. � 'I J . y age 27 of V 4 � a E n E E E E U Fes-- U H v 0 O 9 C O U v M N uOj v 2 0 p b v v S Q In V+ v+ 1n Y+ Q Z Q C Y V Q? V y C C C p= r0/1 N 0 Z 0 Z 0 Z 0= Z Z Z A4 W= o w Z Z 'I J . y age 27 of V 4 � a E n E E E E U Fes-- U H v 0 O 9 C cCd � z v M N O p b Q P 0 0 p b v � Q In V+ v+ 1n Y+ 00 0 a Q C Y V v± V M � 'I J . y age 27 of V 4 � a E n E E E E U Fes-- U H v 0 C cCd � z jn� b N aJ -0 § b cz�zp Q C 'I J . y age 27 of V 4 � a E n E E E E U Fes-- U H v 0 M 00 M 00 MO N 't N�. C N P. fs. u o y N. U Q O q � 0 0 +rp 't_ a+ o y -Bu- � cw� z ✓-' n � u m N t� N O N +� _ O N � N a N � N C N O N y, V d N N N_ N N N N N ',D N N N C N N N N CL E a E E E U H age 28 of E E n E E U H 7� V �y 0 t o 0 N fn fn fn Cl) fn N N fn US 00 cL N y L cw cC N Q Q N LL C C N fA Q N ►L C C fn U CS 00 �• u o Z O A y cw � 0 D O .� v� zCL o- ja ►� °° 0 ° .0 y F � x v w O a a) yam^ N ( C ~ Q W .0 W P4 U U U Cl) Q Z d c c c QZ_ _ c c c Z °� a ~= w 0 N M Z Z Z p= w 0 N M Z Z E E F= v Z 4) O = Z � o 0 Y I 1 V v v b ` Tw S 00 N00 Ito O� �� �rTs p00�0 "� � •� 2 a 40 1<0�<� 0z�J�/Jy z1� �fJArac co U Al H c o v a cn 0 J/ 5 05 g 29 of 31 `Matrix: Air, Freshwater (FVV), seawater (SM, groundwater (GVV , wastewater (WV47,-soil (SL), sediment (SD), tissue (T5), product (P), other (0) Rev 1.1 (April 2005) 18804 Northereek Parkway Phone (425) 483-3300 Bothell, WA 98011 Fax (425) 483-9818 �wwYwru� war+aiai c+arw" Com an Name: BRL Project Manager: Jeremyi4iaute Contact Person: By submitting of samples the client agrees to all terms and conditions set forth ddress:+.j Z C7 in the quotation provided by the BRI.. project manager. If you are not fatniliar r Ot C 0 1 with the term and conditions associated with your project, please contact your Phone Number - - 1111 BRI, representative as soon as possible 425 483-3300. Fax Number; Requested Turn Around "fime: P:ma.il Address: {�{-i , . c Q.,,, Method of Sample Delivery: Project Name; Ile, ,,., Courier Tracking Number: Project Number: 6. 107. I.# � Confirmation of Sample Reception: Yes 13 No Q Number: 121`7608 Sam It TD Bottle TD Date and Time Matrix* Volume Preservative Initials Requested Anal tcs and Methods Comments ALLr71 s -'a -t2 t 15 a M S1 -L EDTA -1 As S ec field filtered o fZftm,NH4OHINH4804 Cr(VlJ field filtered • 14r, z> /16 Degassed HCI Fe Spec field filtered a ItOf L None Mn Spec field filtered .+`kIgir, o 1ur . L None Mn S ec unfiltered -zc -s qnr- w.fx JZS' L None Se Spec field filtered EDTA - I As Spec field filtered NH4OH/NH4SO4 Cr VI field filtered Degassed HCl Fe Spec field filtered None Mn Spec field filtered None Mn Spec unfiltered None Se Spec field filtered Relinquished by: (sign) DIint) -,>M, I y , ��� fp 0C Date/Time: /.-"/0 comments: Received by: (sign) pint)_ . CL -C 1L DatelTime:-. Temp: soc-- Comments: Relinquished by: (sign) (print) Date/Time: Received by: (sin (printlin Date/Time: Temp: Please account for eaiLh samnie ISnttle av a 9AMO it& int srrri�ral;— n. --o iitMm `Matrix: Air, Freshwater (FVV), seawater (SM, groundwater (GVV , wastewater (WV47,-soil (SL), sediment (SD), tissue (T5), product (P), other (0) Rev 1.1 (April 2005) -oject Name: M&)fj L1S .oject Number: ij b:LitK_ D Number. ttnplc ID III X111 BIM'W, bg ,b b,{ +Ir Ai3lmW'w 45 g S s A��y1W-�5 S elinqui�shed�by'. (sign) eceived by: (sign) 1,217608 i field filtered None ru, Bottle ID Date and Time Matrix* Volume I Preservative S�IOD�1Q Sato iS 10141" Cr(VI) EDTA -1 r cb, re time 1632. None NH4OH/NH4SO4 Im JLOt ell < IMM f�ia� Deaassed HCI S&hs field filtered None ru, Mn Spec EDTA -1 �6L t5 tt}3 field filtered NH4OH1NH4SO4 d it1 Cr(VI) De assed HCI r cb, re time Il None 18804 Nosthereek Parkway Phone (425) 483-3300 Bothell, WA 98011 Fax (425) 483.9818 By submitting of sampLes the client agrees to all team and conditions set forth in the quotation provided by the BRL project manager. If you are not familiar with the term and conditions associated with your project, please contact your BRI, re resentative as soon as possible'(U5 483-3300. Requested Turn Around Tune: Method o£ Sample Delivery Courier Tracksn Number: Confirmation of Sample Reception: 'Yes ® No Ittitilk R nested Analytes and Methods Comments As Spec Meld filtered /., G VII field filtered DaterTme:;Q�, 1 IUD Relinquished by: (sign) (p(nt) Datell ime:_„ _ — Received by (sign) (print) Date/Time: Please account for each sample bottle as a seperate line item for verification purposes. Matrix: Air, Freshwater (['Vii), seawater (9114'), groundwater (GV), wastewater (W W), soil (SL), sediment (SD), tissue (I'S), product (P), other (0) Fe Spec field filtered Mn Spec field filtered Mn Spec unfiltered Se Spec field filtered As Spec field filtered Cr(VI) field filtered Fe Spec field filtered Mn Spec field filtered Mn Spec _ unfiltered Se Spec field filtered A100 Rev 1.1 (April 2005) 0 P� []r i AB IMIKMNkN4iYyk. MiTJ.{l.f OATA 18804 Northcreek Parkway Phone (425) 483-3300 Bothell, WA 98011 Fax (425) 483-9818 Company Name: li A,, BRL Proi ct Manager: Jeremy Maute Contact Person: T@A '�Wm& Address: %!A- i-e*.w4(i©l Phone Number: 149,x, By submitting of samples the client agrees to all terms and conditions set forth lin the quotation provided by the BRL project manager. If you are not familiar with the term and conditions associated with your project, please contact your BRL representative as soon as possible 425 483-3300, Fax Number. Requested Turn Around Time: Email Address: "r 3q,=iutecor , CQrpn Method of SanVIe Deliverr. GA e Pro' ct Name: MA),ok9g Courier Tracking Number: Pro' ct Number: 102fA, PO Number: log, 1.1 1217648 Confirmation of Sample Reception: Ys ® No Sample ID Bottle ID Date and Time Matrix* Volurne Preservative Initials Requested Analytes and Methods Comments •A CLRAII O.Lk$ w W -C y(�0 S1 25 1 5 EDTA -1 NH40H/NH4SO4 As Spec field filtered Cr(yl) field filtered 1 Degassed HCI Fe Spec field filtered N � 141W,04: 61 (as l 2a S IRS None Mn Spec field filtered • M111-04 3°I' S s lS 1 L None Mn S ec unfiltered zgopsl None. Se Spec field filtered A144, OSJI • �j(gi,,a 1'vsL �:.l !a �, EDTA -1 NH40H/NH4SO4 As Spec field filtered . Cr(VI) field filtered M -OS $'bol'squ 1141$' Cti 125 VAL, Degassed HCI .. Fe Spec field filtered 35 s '1041B' 12,5b%L None Mn Spec field filtered �►- �r395 s 1 N12( 12 None Mn Spec unfiltered 1�J- 5 1':1'?jl 1y1gIJ None Se Spec field filtered Relinquished by. {sign) {print} Received by: (sign) (print) 2�k c: . k Date/Time: Dateffime: comments: � 130 Temp: Relinquished by: (sign) Received by: (sign) (print) (print) Dateffime: Date/Time: Comments: Temp Please account for each sample bottle as a seperate line item for verification purposes. "%Aatdx: Air,, Freshwater (FW[ , seawater (SW), groundwater (GVV), wastewater (VAV� soil (SI.), sediment (SD), tissue CrS), product (13), other (0) ttev t.t (April 2005)